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ES2572769T3 - Curable powder coating compositions that provide improved scratch and abrasion resistance and method of use thereof - Google Patents

Curable powder coating compositions that provide improved scratch and abrasion resistance and method of use thereof Download PDF

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Publication number
ES2572769T3
ES2572769T3 ES01273637.7T ES01273637T ES2572769T3 ES 2572769 T3 ES2572769 T3 ES 2572769T3 ES 01273637 T ES01273637 T ES 01273637T ES 2572769 T3 ES2572769 T3 ES 2572769T3
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sample
particles
paper
samples
powder coating
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John R. Schneider
Deirdre D. Ragan
Karen S. Rechenberg
Anthony M. Chasser
Karen A. Barkac
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PPG Industries Ohio Inc
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PPG Industries Ohio Inc
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04Homopolymers or copolymers of esters
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/66Additives characterised by particle size
    • C09D7/68Particle size between 100-1000 nm
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/66Additives characterised by particle size
    • C09D7/69Particle size larger than 1000 nm
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/01Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013Fillers, pigments or reinforcing additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/10Metal compounds
    • C08K3/14Carbides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/14Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/18Spheres

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
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  • Paints Or Removers (AREA)

Abstract

Una composición de revestimiento en polvo curable que comprende: una resina formadora de película que comprende al menos un polímero que tiene al menos un tipo de grupo funcional reactivo y un agente de curado que tiene grupos funcionales reactivos con el grupo funcional del polímero; y una pluralidad de partículas inorgánicas seleccionadas entre partículas de alúmina que tienen un tamaño medio de partícula comprendido entre 0,1 y 6 μm y partículas de carburo de silicio que tienen un tamaño medio de partícula comprendido entre 0,1 y 10 μm dispersadas en dicha resina en una cantidad del 0,1 al 8 por ciento en peso en base al peso total de la composición de revestimiento.A curable powder coating composition comprising: a film-forming resin comprising at least one polymer having at least one type of reactive functional group and a curing agent having functional groups reactive with the polymer functional group; and a plurality of inorganic particles selected from alumina particles having an average particle size between 0.1 and 6 μm and silicon carbide particles having an average particle size between 0.1 and 10 μm dispersed therein resin in an amount of 0.1 to 8 percent by weight based on the total weight of the coating composition.

Description

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Las composiciones de revestimiento en polvo se aplican más frecuentemente mediante pulverización, y en el caso de un sustrato metálico, mediante pulverización electrostática, o mediante el uso de un lecho fluidizado. El revestimiento en polvo puede aplicarse en un único barrido o en varias pasadas para proporcionar una película que tiene un espesor después del curado de 25 a 250 μm (de 1 a 10 milésimas de pulgada), normalmente de 50 a 100 μm. Pueden emplearse otros procedimientos estándar para la aplicación de revestimientos tal como cepillado, inmersión o flujo. Powder coating compositions are applied more frequently by spraying, and in the case of a metal substrate, by electrostatic spraying, or by using a fluidized bed. The powder coating can be applied in a single scan or in several passes to provide a film having a thickness after curing of 25 to 250 μm (1 to 10 thousandths of an inch), usually 50 to 100 μm. Other standard procedures for the application of coatings such as brushing, dipping or flow can be employed.

Las composiciones líquidas de la invención pueden ser aplicadas también mediante cualquier procedimiento convencional tal como cepillado, inmersión, revestimiento por flujo, revestimiento con rodillo, pulverización convencional y electrostática. Más frecuentemente, se usan técnicas de pulverización. Típicamente, el espesor de película para los revestimientos líquidos puede variar entre 2,5 y 127 μm, tal como entre 2,5 y 25,4 μm, o de aproximadamente 10,2 μm. The liquid compositions of the invention can also be applied by any conventional method such as brushing, immersion, flow coating, roller coating, conventional and electrostatic spraying. More frequently, spray techniques are used. Typically, the film thickness for liquid coatings can vary between 2.5 and 127 μm, such as between 2.5 and 25.4 μm, or approximately 10.2 μm.

Generalmente, después de la aplicación de la composición de revestimiento, el sustrato revestido se cuece a una temperatura suficiente para curar el revestimiento. Los sustratos metálicos con revestimientos en polvo se curan típicamente a una temperatura que varía de 121,1°C a 260,0°C durante 1 a 60 minutos, o de 148,9°C a 204,4°C durante 15 a 30 minutos. Generally, after application of the coating composition, the coated substrate is baked at a temperature sufficient to cure the coating. Powder coated metal substrates are typically cured at a temperature ranging from 121.1 ° C to 260.0 ° C for 1 to 60 minutes, or 148.9 ° C to 204.4 ° C for 15 to 30 minutes

Varias formulaciones líquidas pueden curarse a temperatura ambiente, tales como las que usan un agente de curado poliisocianato o polianhídrido, o pueden curarse a temperaturas elevadas para acelerar la cura. Un ejemplo sería el curado con aire forzado en una cabina con corriente de aire descendente a aproximadamente entre 40°C y 60°C, que es común en la industria de acabado de automóviles. Las composiciones curables a temperatura ambiente normalmente se preparan como sistema de dos (2) envases en el que el agente de curado se mantiene separado del polisiloxano que contiene el grupo funcional reactivo. Los paquetes se combinan poco antes de la aplicación. Several liquid formulations can be cured at room temperature, such as those using a polyisocyanate or polyanhydride curing agent, or they can be cured at elevated temperatures to accelerate the cure. An example would be forced air curing in a cabin with downward air flow at approximately 40 ° C to 60 ° C, which is common in the automobile finishing industry. Compositions curable at room temperature are usually prepared as a system of two (2) packages in which the curing agent is kept separate from the polysiloxane containing the reactive functional group. The packages are combined shortly before application.

Las composiciones líquidas curables térmicamente, tales como las que usan isocianato bloqueado, aminoplasto, fenoplasto, poliepóxido o agente de curado de poliácido pueden prepararse como un sistema de un paquete. Estas composiciones se curan a temperaturas elevadas, típicamente durante 1 a 30 minutos a 121°C a 232°C con la temperatura dependiendo principalmente del tipo de sustrato usado. El tiempo de permanencia (es decir, el tiempo que el sustrato revestido está expuesto a temperatura elevada para el curado) depende de las temperaturas de curado usadas, así como del espesor de película húmeda de la composición de revestimiento aplicada. Por ejemplo, las piezas elastoméricas de automoción revestidas requieren un largo tiempo de permanencia a una temperatura de cura inferior (por ejemplo, 30 minutos a 121°C (250°F), mientras que los envases de bebidas de aluminio revestidos requieren un tiempo de permanencia muy corto a una temperatura de curado muy alta (por ejemplo, 1 minuto a 191°C). Thermally curable liquid compositions, such as those using blocked isocyanate, aminoplast, phenoplast, polyepoxide or polyacid curing agent can be prepared as a package system. These compositions are cured at elevated temperatures, typically for 1 to 30 minutes at 121 ° C to 232 ° C with the temperature depending mainly on the type of substrate used. The residence time (ie, the time that the coated substrate is exposed to high temperature for curing) depends on the curing temperatures used, as well as the wet film thickness of the applied coating composition. For example, coated automotive elastomeric parts require a long residence time at a lower cure temperature (for example, 30 minutes at 121 ° C (250 ° F), while coated aluminum beverage containers require a shelf life of very short stay at a very high cure temperature (for example, 1 minute at 191 ° C).

Las composiciones de revestimiento de la invención son particularmente útiles como imprimaciones y como capas de color y/o transparentes en revestimientos compuestos de color-transparentes. Las composiciones de la invención en forma pigmentada pueden aplicarse directamente a un sustrato para formar una capa de color. La capa de color puede estar en la forma de un imprimador para la posterior aplicación de una capa de acabado o puede ser una capa de acabado de color. De manera alternativa, la composición de revestimiento de la invención puede ser no pigmentada, en la forma de una capa transparente para su aplicarse sobre una capa de color (bien una capa de imprimación o una capa de acabado de color). Cuando se usa como un revestimiento de imprimación, los espesores de 10,2 a 101,6 μm son típicos. Cuando se usa como una capa de acabado de color, los espesores de revestimiento de aproximadamente 12,7 a 101,6 μm son típicos, y cuando se usa como una capa transparente, generalmente se usan espesores de revestimiento de aproximadamente 38,1 a 101,6 μm. The coating compositions of the invention are particularly useful as primers and as color and / or transparent layers in color-transparent composite coatings. The compositions of the invention in pigmented form can be applied directly to a substrate to form a color layer. The color layer may be in the form of a primer for the subsequent application of a finishing layer or it may be a color finishing layer. Alternatively, the coating composition of the invention can be non-pigmented, in the form of a transparent layer to be applied on a color layer (either a primer layer or a color finish layer). When used as a primer coating, thicknesses of 10.2 to 101.6 μm are typical. When used as a color finishing layer, coating thicknesses of approximately 12.7 to 101.6 μm are typical, and when used as a transparent layer, coating thicknesses of approximately 38.1 to 101 are generally used. , 6 μm.

Por consiguiente, la presente invención está dirigida además a un sustrato revestido con una o más de las presentes composiciones. Los substratos y composiciones, y la manera de aplicación de las mismas, son tal como se ha descrito anteriormente. Accordingly, the present invention is further directed to a substrate coated with one or more of the present compositions. The substrates and compositions, and the manner of application thereof, are as described above.

La presente invención se refiere además a una composición de revestimiento compuesto de múltiples capas que comprende una capa base depositada desde una composición formadora de película y una capa de acabado aplicada sobre al menos una parte de la capa base, donde la capa de acabado se deposita desde cualquiera de las composiciones de revestimiento de la presente invención. La capa base podría tener un espesor de película curada de entre 12,5 y 100 μm, mientras que el espesor de la película de la capa de acabado curada puede ser de hasta 250 μm. La capa base puede ser curada antes de la aplicación de la capa de acabado, o las dos capas pueden ser curadas juntas. En un ejemplo, la capa base puede ser depositada desde una composición formadora de película pigmentada, mientras que la capa de acabado formada a partir de las presentes composiciones es substancialmente transparente. Este es el sistema colormás-transparente descrito anteriormente, que se usa frecuentemente en aplicaciones de automoción. The present invention further relates to a multi-layer composite coating composition comprising a base layer deposited from a film-forming composition and a finishing layer applied to at least a part of the base layer, where the finishing layer is deposited. from any of the coating compositions of the present invention. The base layer could have a cured film thickness between 12.5 and 100 μm, while the film thickness of the cured finish layer can be up to 250 μm. The base coat can be cured before the application of the finish coat, or the two layers can be cured together. In one example, the base layer can be deposited from a pigmented film forming composition, while the finishing layer formed from the present compositions is substantially transparent. This is the color-transparent system described above, which is frequently used in automotive applications.

En todavía otra realización, la presente invención se refiere a un procedimiento para mejorar el resistencia a la abrasión y/o al rayado de un substrato revestido que comprende la aplicación de las presentes composiciones a al menos una parte del sustrato. La aplicación puede ser mediante cualquier medio conocido en la técnica para los espesores descritos anteriormente. In yet another embodiment, the present invention relates to a process for improving the abrasion and / or scratch resistance of a coated substrate comprising the application of the present compositions to at least a portion of the substrate. The application can be by any means known in the art for the thicknesses described above.

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Los revestimientos formados según la presente invención tienen excelentes propiedades de apariencia y propiedades de resistencia a la abrasión y al rayado en comparación con los revestimientos sin partículas presentes. Se ha descubierto sorprendentemente que las composiciones de la presente invención resultan en revestimientos que tienen una excepcional resistencia a la degradación UV. Por consiguiente, la invención se refiere además a un revestimiento curado que tiene partículas dispersas en el mismo, tal como un revestimiento en polvo, que tiene menos del 10 por ciento, tal como menos del 5 por ciento o incluso menos del 4 por ciento, de reducción del brillo después de 500, 1.000 y 1.500 horas de exposición QUV. Tal como se muestra en los Ejemplos siguientes, los revestimientos de la presente invención incluso pueden haber mejorado la resistencia después de la exposición QUV. La expresión "exposición QUV" se refiere a cualquier tipo de exposición QUV, tal como los ensayos realizados según ASTM D-4587. The coatings formed according to the present invention have excellent appearance properties and abrasion and scratch resistance properties compared to the coatings without particles present. It has surprisingly been discovered that the compositions of the present invention result in coatings that have exceptional resistance to UV degradation. Accordingly, the invention further relates to a cured coating having dispersed particles therein, such as a powder coating, having less than 10 percent, such as less than 5 percent or even less than 4 percent, brightness reduction after 500, 1,000 and 1,500 hours of QUV exposure. As shown in the following Examples, the coatings of the present invention may even have improved strength after QUV exposure. The term "QUV exposure" refers to any type of QUV exposure, such as tests performed according to ASTM D-4587.

Tal como se usa en la presente memoria, a menos que se especifique expresamente lo contrario, todos los números tales como los que expresan valores, intervalos, cantidades o porcentajes pueden leerse como si estuvieran precedidos por la palabra "aproximadamente", aunque el término no aparezca expresamente. También, cualquier intervalo numérico citado en la presente memoria pretende incluir todos los subintervalos incluidos en el mismo. Tal como se usa en la presente memoria, el término "polímero" se refiere a oligómeros y tanto a homopolímeros como a copolímeros. As used herein, unless expressly stated otherwise, all numbers such as those expressing values, intervals, quantities or percentages may be read as if they were preceded by the word "approximately", although the term does not Appear expressly. Also, any numerical range cited herein is intended to include all subintervals included therein. As used herein, the term "polymer" refers to oligomers and both homopolymers and copolymers.

Ejemplos Examples

Para todos los ejemplos, a menos que se indique lo contrario, se midió el brillo a 20º con un medidor de brillo estadístico portátil 20° NOVO-GLOSS 20, disponible en Gardener Instrument Company, Inc. For all examples, unless otherwise indicated, the brightness was measured at 20 ° with a portable statistical brightness meter 20 ° NOVO-GLOSS 20, available from Gardener Instrument Company, Inc.

Se llevó a cabo un ensayo de resistencia al rayado BON AMI ("BON AMI") usando un dispositivo Atlas AATCC Mar Tester Model CM-5, disponible en Atlas Electrical Devices Co. de Chicago, Illinois. Con un paño de fieltro anclado al dedo acrílico sobre el brazo del instrumento, se llevaron a cabo un conjunto de 10 frotamientos dobles (a menos que se indique lo contrario) sobre cada panel, que se revistió con limpiador BON AMI. A continuación, el panel se lavó con agua fría del grifo y se secó. En las tablas siguientes, la resistencia a la abrasión se expresa como un porcentaje del brillo a 20º que se retuvo después de que la superficie fuera sometida a abrasión por el dispositivo de ensayo de abrasión. La resistencia a la abrasión se midió como: Resistencia a la abrasión = (Brillo después de abrasión ÷ Brillo original) x 100. A BON AMI ("BON AMI") scratch resistance test was carried out using an Atlas AATCC Mar Tester Model CM-5 device, available from Atlas Electrical Devices Co. of Chicago, Illinois. With a felt cloth anchored to the acrylic finger on the arm of the instrument, a set of 10 double rubs (unless otherwise indicated) were carried out on each panel, which was coated with BON AMI cleaner. Next, the panel was washed with cold tap water and dried. In the following tables, the abrasion resistance is expressed as a percentage of the brightness at 20 ° which was retained after the surface was subjected to abrasion by the abrasion test device. Abrasion resistance was measured as: Abrasion resistance = (Gloss after abrasion ÷ Original gloss) x 100.

También se llevó a cabo un ensayo de resistencia al rayado con papel abrasivo 1, 2 y 9μ 3M ("papel 1, 2 o 9μ") usando el dispositivo de ensayo Atlas. Una pieza de 5,08 cm x 5,08 cm (2" x 2") de papel abrasivo 3M respaldado con paño de fieltro se ancló al dedo acrílico sobre el brazo del instrumento, y se llevaron a cabo un conjunto de 10 frotamientos dobles (a menos que se indique lo contrario) sobre cada panel. A continuación, el panel se lavó con agua fría del grifo y se secó. En las tablas siguientes, la resistencia al rayado se expresa como el porcentaje del brillo a 20° que se conserva después del rayado de la superficie por el dispositivo de ensayo de rayado. La resistencia al rayado se midió como: Resistencia al rayado = (Brillo después del rayado ÷ Brillo original) x 100. A scratch resistance test with abrasive paper 1, 2 and 9μ 3M ("paper 1, 2 or 9μ") was also carried out using the Atlas test device. A piece of 5.08 cm x 5.08 cm (2 "x 2") of 3M abrasive paper backed with felt cloth was anchored to the acrylic finger on the instrument arm, and a set of 10 double rubs were carried out (unless otherwise indicated) on each panel. Next, the panel was washed with cold tap water and dried. In the following tables, the scratch resistance is expressed as the percentage of brightness at 20 ° that is retained after the surface is scratched by the scratch test device. Scratch resistance was measured as: Scratch resistance = (Brightness after scratch ÷ Original brightness) x 100.

La turbidez BYK Gardner se midió usando el Instrumento BYK/Haze Gloss siguiendo las instrucciones del fabricante. BYK Gardner turbidity was measured using the BYK / Haze Gloss Instrument following the manufacturer's instructions.

También se llevaron a cabo ensayos de lana de acero usando el dispositivo Atlas Tester ("lana de acero") de la misma manera que los ensayos de rayado, usando solo una pieza de 5,08 cm x 5,08 cm (2" x 2") de la hoja de lana de acero de grado 0000# respaldada con paño de fieltro. Steel wool tests were also carried out using the Atlas Tester device ("steel wool") in the same way as the scratch tests, using only one piece of 5.08 cm x 5.08 cm (2 "x 2 ") of 0000 # grade steel wool sheet backed with felt cloth.

Los ensayos de lana de acero se llevaron a cabo también usando un martillo ligero (571 gramos "martillo ligero") o un martillo pesado (1.381 gramos "martillo pesado") envuelto con lana de acero grado 0000#. En algunos casos, el martillo pesado tenía un peso de 1.382 gramos montado sobre la parte superior. Por lo demás, estos ensayos se llevaron a cabo tal como se ha descrito anteriormente para los ensayos de rayado. Los valores reparados en las tablas siguientes para los ensayos de lana de acero representan porcentajes de retención de brillo. Steel wool tests were also carried out using a light hammer (571 grams "light hammer") or a heavy hammer (1,381 grams "heavy hammer") wrapped with 0000 # grade steel wool. In some cases, the heavy hammer had a weight of 1,382 grams mounted on top. Otherwise, these tests were carried out as described above for the scratch tests. The values repaired in the following tables for steel wool tests represent gloss retention percentages.

Los ejemplos siguientes pretenden ilustrar la invención, y no deberían interpretarse en modo alguno como limitativos de la invención. The following examples are intended to illustrate the invention, and should not be construed in any way as limiting the invention.

Ejemplo 1 Example 1

Las composiciones de revestimiento en polvo, epoxi-ácido, transparentes, identificadas como Muestras 1 a 7 en la Tabla I se prepararon usando los componentes y las cantidades (partes en peso) mostrados, y se procesaron de la siguiente manera. Los componentes se mezclaron en un dispositivo Henschel Blender durante 60 a 90 segundos. A continuación, las mezclas se extruyeron en una extrusora de doble tornillo con co-rotación Werner & Pfleider a una velocidad de tornillo de 450 RPM y a una temperatura de producto extruido de 100°C a 125°C. A continuación, el material extruido se molió a un tamaño de partícula de 17 a 27 μm usando una amoladora ACM (Air Classifying Mill de Micron Powder Systems, Summit, Nueva Jersey). Los paneles de ensayo de acero laminados en frío se revistieron con PPG Black Electrocoat primer ED5051, se curaron completamente, y se obtuvieron en ACT Laboratories. Los polvos terminados se pulverizaron electrostáticamente sobre paneles de ensayo y se evaluaron para determinar las propiedades de los revestimientos tal como se describe a continuación. The transparent, epoxy-acid powder coating compositions identified as Samples 1 to 7 in Table I were prepared using the components and amounts (parts by weight) shown, and processed as follows. The components were mixed in a Henschel Blender device for 60 to 90 seconds. The mixtures were then extruded in a double screw extruder with Werner & Pfleider co-rotation at a screw speed of 450 RPM and at an extruded product temperature of 100 ° C to 125 ° C. Next, the extrudate was ground to a particle size of 17 to 27 μm using an ACM grinder (Air Classifying Mill from Micron Powder Systems, Summit, New Jersey). Cold-rolled steel test panels were coated with PPG Black Electrocoat primer ED5051, completely cured, and obtained from ACT Laboratories. The finished powders were electrostatically sprayed onto test panels and evaluated to determine the properties of the coatings as described below.

imagen7image7

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Los revestimientos en polvo de las Muestras 1-7 se aplicaron a entre 58 y 71 μm (2,3 a 2,8 milésimas de pulgada) y se curaron durante 30 minutos a 145°C (293°F). A continuación, los paneles se sometieron a los ensayos de abrasión y rayado indicados en las tablas siguientes. Se prepararon una serie de paneles de control. En general, las Muestras 2-7, que representan las composiciones según la presente invención, se comportaron mejor en todos los ensayos en comparación con la Muestra 1, que no incluía las presentes partículas. The powder coatings of Samples 1-7 were applied at between 58 and 71 μm (2.3 to 2.8 thousandths of an inch) and cured for 30 minutes at 145 ° C (293 ° F). Next, the panels were subjected to the abrasion and scratch tests indicated in the following tables. A series of control panels were prepared. In general, Samples 2-7, which represent the compositions according to the present invention, performed better in all tests compared to Sample 1, which did not include the present particles.

Tabla 2 Table 2

Ensayo de resistencia a la abrasión/al rayado Abrasion / Scratch Resistance Test
Muestra 1 de control Muestra 2* 0,1% de polvo de diamante Muestra 6* 1,0% de Sunspheres Muestra 7* 0,3% de Zeeospheres W-210 Sample 1 of control Sample 2 * 0.1% diamond dust Sample 6 * 1.0% of Sunspheres Sample 7 * 0.3% of Zeeospheres W-210

BON AMI BON AMI
57 61 79 83 57 61 79 83

Papel 1μ 1μ paper
63 90 67 86 63 90 67 86

Papel 2μ 2μ paper
52 91 63 72 52 91 63 72

Papel 9μ 9μ paper
8 67 8 9 8 67 8 9

* No es un ejemplo de la presente invención * Not an example of the present invention

Los resultados de la Tabla 2 demuestran que las partículas no uniformes presentes en una concentración tan baja como el 0,1 por ciento en peso proporcionan una mejor protección contra la abrasión y el rayado (Muestra 2); la mejora se observa también con partículas esféricas (Muestras 6 y 7). The results in Table 2 demonstrate that non-uniform particles present in a concentration as low as 0.1 percent by weight provide better protection against abrasion and scratching (Sample 2); the improvement is also observed with spherical particles (Samples 6 and 7).

Tabla 3 Table 3

Ensayo de resistencia a la abrasión/al rayado Abrasion / Scratch Resistance Test
Muestra 3* 0,3% de Zeeospheres 610 Muestra 1 de control Sample 3 * 0.3% of Zeeospheres 610 Sample 1 of control

BON AMI BON AMI
73 61 73 61

Papel 1μ 1μ paper
88 55 88 55

Papel 9μ 9μ paper
15 8 fifteen 8

* No es un ejemplo de la presente invención * Not an example of the present invention

Los resultados de la Tabla 3 demuestran una resistencia mejorada con partículas que tienen un tamaño de partícula promedio de 10μ (Muestra 3). The results in Table 3 demonstrate improved resistance with particles having an average particle size of 10μ (Sample 3).

15 Tabla 4 15 Table 4

Ensayo de resistencia a la abrasión/al rayado Abrasion / Scratch Resistance Test
Muestra 4 0,3% de WCA-3 Muestra 5 0,3% WCA-3 + 1, 0% Sunspheres 05 Muestra 1 de control Sample 4 0.3% of WCA-3 Sample 5 0.3% WCA-3 + 1, 0% Sunspheres 05 Sample 1 of control

BON AMI BON AMI
88 98 57 88 98 57

Papel 1μ 1μ paper
94 96 47 94 96 47

Papel 2μ 2μ paper
90 89 50 90 89 fifty

Papel 9μ 9μ paper
21 13 6 twenty-one 13 6

Los resultados de la Tabla 4 demuestran que puede usarse también una mezcla de partículas para mejorar la resistencia a la abrasión y al rayado. La mezcla de partículas (Muestra 5) proporcionó resultados, en particular para la resistencia a la abrasión, mejorados en comparación con los obtenidos con las partículas individuales, Muestra 4 y Muestra 6 (mostrados en la Tabla 2). En todos los casos, el uso de las partículas proporcionó una resistencia a la abrasión mejorada en comparación con el control (Muestra 1). The results in Table 4 demonstrate that a mixture of particles can also be used to improve abrasion and scratch resistance. The mixture of particles (Sample 5) provided results, in particular for abrasion resistance, improved compared to those obtained with the individual particles, Sample 4 and Sample 6 (shown in Table 2). In all cases, the use of the particles provided improved abrasion resistance compared to the control (Sample 1).

12 12

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imagen10image10

Tabla 10 Table 10

Descripción Description
Muestra 15 de control Muestra 16 % en peso de sílice Muestra 17 % en peso de sílice Sample 15 of control Sample 16% by weight silica Sample 17% by weight silica

Resina acrílica GMA14 GMA14 acrylic resin
79,18 77,52 77,52 79.18 77.52 77.52

DDDA DDDA
17,41 17,02 17,02 17.41 17.02 17.02

Benzoína Benzoin
0,38 0,37 0,37 0.38 0.37 0.37

Catalizador trifenil hidróxido de estaño Tin triphenyl hydroxide catalyst
0,98 0,96 0,96 0.98 0.96 0.96

Cera C Micropolvo Wax C Micropolvo
0,53 0,52 0,52 0.53 0.52 0.52

Modaflow15 Modaflow15
0,90 0,88 0,88 0.90 0.88 0.88

Goresil 21016 Goresil 21016
- 2,21 -- - 2.21 -

Goresil2517 Goresil2517
- - 2,21 - - 2.21

14Almatex PD 9060 producido por Anderson Development Company. 15Modaflow, un aditivo de flujo copolímero acrílico aditivo anti-cráteres disponible comercialmente en Solutia, Inc. 16Partículas de sílice, tamaño medio de partícula 2μ, tamaño de partícula máximo 10μ, disponible comercialmente en C.E.D. Process Minerals, Inc. 17Partículas de sílice, tamaño medio de partícula 2μ, tamaño de partícula máximo 5 μm, disponible comercialmente en C. E. D. Process Minerals, Inc. 14Almatex PD 9060 produced by Anderson Development Company. 15 Modaflow, a flow additive acrylic copolymer additive anti-craters commercially available from Solutia, Inc. 16 Silica particles, average particle size 2μ, maximum particle size 10μ, commercially available from C.E.D. Process Minerals, Inc. 17 Silica particles, average particle size 2μ, maximum particle size 5 μm, commercially available from C. E. D. Process Minerals, Inc.

Los paneles revestidos con las Muestras 15-17 se sometieron al BON AMI y los ensayos de lana de acero descritos anteriormente. Los resultados se presentan en la Tabla 11. La retención de brillo, es decir, la resistencia, se mejoró en gran medida con las dos sílices; la sílice más pequeña (Muestra 17) proporcionó un valor de turbidez que es más deseable en una aplicación de capa transparente sin comprometer el rendimiento. Panels coated with Samples 15-17 were submitted to the BON AMI and the steel wool tests described above. The results are presented in Table 11. The gloss retention, that is, the resistance, was greatly improved with the two silicas; The smaller silica (Sample 17) provided a turbidity value that is more desirable in a transparent coat application without compromising performance.

Tabla 11 Table 11

Descripción Description
Muestra 15 Muestra 16 Muestra 17 Sample 15 Sample 16 Sample 17

Brillo inicial a 20º Initial brightness at 20º
83 79 82 83 79 82

Turbidez BYK Gardner Turbidity BYK Gardner
36 84 39 36 84 39

Bon Ami (20 frotamientos dobles) Bon Ami (20 double rubs)
82 98 98 82 98 98

Frotamientos dobles con lana de acero de grado 0000# (10x, martillo ligero) Double rubs with 0000 # grade steel wool (10x, light hammer)
57 96 91 57 96 91

Frotamientos dobles con lana de acero de grado 0000# (5x, martillo ligero) Double rubs with 0000 # grade steel wool (5x, light hammer)
74 97 95 74 97 95

Ejemplo 6 Example 6

Las Muestras 18-21 se prepararon y se ensayaron como las del Ejemplo 5, usando los componentes y los porcentajes en peso mostrados en la Tabla 12. Samples 18-21 were prepared and tested as in Example 5, using the components and weight percentages shown in Table 12.

15 fifteen

Tabla 12 Table 12

Descripción Description
Muestra 18 Muestra 19 Muestra 20 Muestra 21 Sample 18 Sample 19 Sample 20 Sample 21

Resina acrílica GMA GMA acrylic resin
79,76 77,98 - -- 79.76 77.98 - -

Resina Acrílica GMA/IBoMA18 Acrylic Resin GMA / IBoMA18
- - 81,63 83,49 - - 81.63 83.49

DDDA DDDA
17,51 17,12 13,48 13,78 17.51 17,12 13.48 13.78

Benzoína Benzoin
0,38 0,38 0,37 0,38 0.38 0.38 0.37 0.38

Catalizador trifenil hidróxido de estaño Tin triphenyl hydroxide catalyst
0,91 0,89 0,89 0,91 0.91 0.89 0.89 0.91

Micropolvo Cera C Micropowder Wax C
0,53 0,52 0,52 0,53 0.53 0.52 0.52 0.53

Modaflow Modaflow
0,91 0,89 0,89 0,91 0.91 0.89 0.89 0.91

Goresil 25 Goresil 25
- 2,22 2,22 - - 2.22 2.22 -

18Copolímero acrílico con 40% de metacrilato de glicidilo y 60% de metacrilato de isobornilo 18 Acrylic polymer with 40% glycidyl methacrylate and 60% isobornyl methacrylate

Las Muestras 18 y 19 se formularon con resina acrílica GMA y las Muestras 20 y 21 con resina acrílica GMA/IBoMA, que tenía un RI menor que la resina acrílica GMA. Las muestras 19 y 20 contenían Goresil 25, mientras que las Muestras 18 y Samples 18 and 19 were formulated with GMA acrylic resin and Samples 20 and 21 with GMA / IBoMA acrylic resin, which had an RI lower than GMA acrylic resin. Samples 19 and 20 contained Goresil 25, while Samples 18 and

5 21 proporcionaron un control que carecía de partículas. Los resultados en la Tabla 13 demuestran que el valor de Δ turbidez puede reducirse cuando se usa una resina que tiene un RI más cercano al de la partícula usada. La Δ turbidez para la resina GMA (partícula vs. no partícula) era 16, mientras que entonces la turbidez para la resina GMA/IBoMA era sólo de 8. Las muestras que contenían partículas según la presente invención tenían un rendimiento mejorado con relación a las muestras de control. 5 21 provided a control that lacked particles. The results in Table 13 demonstrate that the value of Δ turbidity can be reduced when a resin having an RI closer to that of the particle used is used. The Δ turbidity for the GMA resin (particle vs. non-particle) was 16, while then the turbidity for the GMA / IBoMA resin was only 8. Samples containing particles according to the present invention had improved performance relative to control samples.

10 Tabla 13 10 Table 13

Descripción Description
Muestra 18 Muestra 19 Muestra 20 Muestra 21 Sample 18 Sample 19 Sample 20 Sample 21

Brillo inicial a 20° Initial brightness at 20 °
83 81 79 80 83 81 79 80

Turbidez BYK Gardner Turbidity BYK Gardner
24 40 33 25 24 40 33 25

BON AMI (20x) BON AMI (20x)
50 80 44 33 fifty 80 44 33

BON AMI (40x) BON AMI (40x)
64 85 72 53 64 85 72 53

Frotamientos dobles con lana de acero de grado 0000# (5x, martillo ligero) Double rubs with 0000 # grade steel wool (5x, light hammer)
76 96 75 59 76 96 75 59

Ejemplo 7 (No es un ejemplo según la presente invención) Las Muestras 22-25 se prepararon y ensayaron tal como se ha descrito en el Ejemplo 5 usando los componentes y los porcentajes en peso mostrados en la Tabla 14. 15 Tabla 14 Example 7 (Not an example according to the present invention) Samples 22-25 were prepared and tested as described in Example 5 using the components and weight percentages shown in Table 14. Table 14

Descripción Description
Muestra 22 Muestra 23 Muestra 24 Muestra 25 Sample 22 Sample 23 Sample 24 Sample 25

Resina acrílica GMA GMA acrylic resin
79,76 75,20 69,81 73,72 79.76 75.20 69.81 73.72

DDDA DDDA
17,51 16,51 15,33 16,19 17.51 16.51 15.33 16.19

Benzoína Benzoin
0,38 0,36 0,33 0,35 0.38 0.36 0.33 0.35

Catalizador trifenil hidróxido de estaño Tin triphenyl hydroxide catalyst
0,91 0,86 0,80 0,84 0.91 0.86 0.80 0.84

(Cont.) (Cont.)

Micropolvo Cera C Micropowder Wax C
0,53 0,50 0,46 0,49 0.53 0.50 0.46 0.49

Modaflow Modaflow
0,91 0,86 0,80 0,84 0.91 0.86 0.80 0.84

Goresil 25 Goresil 25
- 5,72 5,31 -- - 5.72 5.31 -

Nanopartículas19 Nanoparticles19
- - 7,17 7,57 - - 7.17 7.57

19Las nanopartículas se obtuvieron de Clariant Corporation y se dispersaron en un material con funcionalidad ácida. 19 The nanoparticles were obtained from Clariant Corporation and dispersed in a material with acid functionality.

Los resultados presentados en la Tabla 15 demuestran que las formulaciones que comprenden sólo partículas de tamaño micrométrico (Muestra 23) y sólo partículas de tamaño nanométrico en siloxano con funcionalidad ácida (Muestra 25) se comportaron mejor que el control, y que el mejor rendimiento global se observó cuando ambas partículas estaban presentes (Muestra 24). The results presented in Table 15 demonstrate that formulations comprising only micrometer-sized particles (Sample 23) and only nano-sized particles in acid-functional siloxane (Sample 25) behaved better than the control, and that the best overall performance It was observed when both particles were present (Sample 24).

Tabla 15 Table 15

Descripción Description
Muestra 22 Muestra 23 Muestra 24 Muestra 25 Sample 22 Sample 23 Sample 24 Sample 25

Brillo inicial a 20° Initial brightness at 20 °
82 77 77 82 82 77 77 82

Papel 9μ 9μ paper
22 33 56 50 22 33 56 fifty

Papel 3μ 3μ paper
38 53 75 77 38 53 75 77

Papel 2μ 2μ paper
77 87 93 81 77 87 93 81

BON AMI (20 veces) BON AMI (20 times)
72 90 93 81 72 90 93 81

Frotamientos dobles con lana de acero de grado 0000# (5x, martillo pesado) Double rubs with 0000 # grade steel wool (5x, heavy hammer)
77 100 96 82 77 100 96 82

Ejemplo 8 Example 8

Las Muestras 26-29 se prepararon usando una resina de poliéster con funcionalidad ácida que contenían los componentes en los pesos mostrados en la Tabla 16. Las Muestras se ensayaron tal como se ha descrito anteriormente, usando solo paneles de acero laminados en frío con un pretratamiento de fosfato de hierro, obtenido de ACT Laboratories. Samples 26-29 were prepared using an acid-functional polyester resin containing the components at the weights shown in Table 16. The Samples were tested as described above, using only cold-rolled steel panels with a pretreatment. of iron phosphate, obtained from ACT Laboratories.

Tabla 16 Table 16

Descripción Description
Muestra 26 Muestra 27* Muestra 28* Muestra 29 Sample 26 Sample 27 * Sample 28 * Sample 29

Albester 515020 Albester 515020
72,80 64,41 64,41 64,41 72.80 64.41 64.41 64.41

TGIC21 TGIC21
5,30 4,69 4,69 4,69 5.30 4.69 4.69 4.69

SCX-81922 SCX-81922
3,04 2,69 2,69 2,69 3.04 2.69 2.69 2.69

PL-20023 PL-20023
1,10 0,97 0,97 0,97 1.10 0.97 0.97 0.97

Benzoína Benzoin
0,80 0,71 0,71 0,71 0.80 0.71 0.71 0.71

KC-59-920024 KC-59-920024
0,45 0,40 0,40 0,40 0.45 0.40 0.40 0.40

KH-97-378825 KH-97-378825
0,35 0,31 0,31 0,31 0.35 0.31 0.31 0.31

Monarch 130023 Monarch 130023
1,56 1,38 1,38 1,38 1.56 1.38 1.38 1.38

(Cont.) (Cont.)

Vansil W-5027 Vansil W-5027
14,60 12,91 12,91 12,91 14.60 12.91 12.91 12.91

Goresil 25 Goresil 25
- 11,53 - -- - 11.53 - -

Goresil 210 Goresil 210
- - 11,53 -- - - 11.53 -

NABALOX 713-1028 NABALOX 713-1028
- - - 11,53 - - - 11.53

* No es un ejemplo según la invención 20Resina de poliéster con funcionalidad ácida, obtenido en McWhorter Technologies. 21Isocianurato de triglicidilo, disponible comercialmente en Cytec Corporation. 22Acrílico con funcionalidad ácida, usado como aditivo anti-cráteres, disponible comercialmente en Johnson Polymer. 23Aditivo de flujo, acrílico de alto peso molecular suspendido en sílice, disponible comercialmente en Eston Chemical, Inc. 24Actiron 32-057, disponible comercialmente en Synthron, Inc. 25Aditivo anti-cráteres, resina de imida hidroxi uretano en polvo. 26Pigmento negro de carbono, disponible comercialmente en Cabot Corporation. 27Extender, wollastonita, disponible comercialmente en R. T. Vanderbilt Company, Inc. 28α-alúmina, tamaño medio de partícula 0,55 μm, disponible comercialmente en Baikowski International. * Polyester resin with acid functionality, obtained from McWhorter Technologies, is not an example according to the invention. 21 Triglycidyl Isocyanurate, commercially available from Cytec Corporation. 22 Acrylic with acid functionality, used as an anti-crater additive, commercially available from Johnson Polymer. 23 Flow additive, high molecular weight acrylic acrylic suspended in silica, commercially available from Eston Chemical, Inc. 24Actiron 32-057, commercially available from Synthron, Inc. 25 Anti-crater additive, hydroxy urethane imide resin powder. 26 Carbon black pigment, commercially available from Cabot Corporation. 27Extend, wollastonite, commercially available from R. T. Vanderbilt Company, Inc. 28α-alumina, average particle size 0.55 μm, commercially available from Baikowski International.

Tabla 17 Table 17

Descripción Description
Muestra 26 Muestra 27* Muestra 28* Muestra 29 Sample 26 Sample 27 * Sample 28 * Sample 29

Brillo inicial a 20° Initial brightness at 20 °
30 26 23 32 30 26 2. 3 32

Turbidez BYK Gardner Turbidity BYK Gardner
486 475 483 479 486 475 483 479

Papel 9μ 9μ paper
32 44 54 46 32 44 54 46

Papel 3μ 3μ paper
64 83 88 84 64 83 88 84

Papel 2μ 2μ paper
104 126 126 117 104 126 126 117

BON AMI (10x) BON AMI (10x)
71 106 99 88 71 106 99 88

Frotamientos dobles con lana de acero de grado 0000# (30x, martillo pesado) Double rubs with 0000 # grade steel wool (30x, heavy hammer)
94 126 135 109 94 126 135 109

*No es una muestra según la invención * It is not a sample according to the invention

5 Tal como se demuestra en la Tabla 17, las Muestras 27-29 se comportaron mejor en todos los ensayos en comparación con el control, la Muestra 26. Una diversidad de tipos de resinas, incluyendo aquellas que contienen pigmentos, son adecuadas para su uso en la presente invención. 5 As shown in Table 17, Samples 27-29 performed better in all trials compared to the control, Sample 26. A variety of resin types, including those containing pigments, are suitable for use. in the present invention.

Ejemplo 9 (No es un ejemplo según la presente invención) Example 9 (Not an example according to the present invention)

Las composiciones de revestimiento líquidas (Muestras 30-32) se prepararon usando los componentes enumerados en la 10 Tabla 18. Liquid coating compositions (Samples 30-32) were prepared using the components listed in Table 18.

Tabla 18 Table 18

Descripción Description
Muestra 30 Muestra 31 Muestra 32 Sample 30 Sample 31 Sample 32

Nanopartículas20 Nanoparticles20
4,50 4,41 4,31 4.50 4.41 4.31

Metil amil cetona30 Methyl Amyl Ketone30
24,30 23,78 23,29 24.30 23.78 23.29

Resina acrílica31 Acrylic Resin31
37,75 36,95 36,18 37.75 36.95 36.18

Disolvente32 Solvent32
5,74 5,62 5,50 5.74 5.62 5.50

Butil cellosolve acetato33 Butyl cellosolve acetate33
1,04 1,02 1,00 1.04 1.02 1.00

Pasta de partículas34 Paste of particles34
- 2,13 4,17 - 2.13 4.17

Reticulante isocianato35 Isocyanate crosslinker35
26,60 26,04 25,49 26.60 26.04 25.49

Catalizador de estaño36 Tin Catalyst36
0,06 0,06 0,06 0.06 0.06 0.06

2930% nanopartículas de sílice/70% de siloxano. 30Eastman Chemicals. 31Resina acrílica con funcionalidad hidroxilo. 32Disolvente Exxate 600 (acetato de hexilo) de Union Carbide. 33Union Carbide. 3463,4% de pasta de partículas preparada mezclando los siguientes:  Goresil 25 56,0 gramos (35,65%)  Metil amil cetona 21,0 gramos (13,37%)  Resina acrílica con funcionalidad hidroxilo 10,0 gramos (3,37%)  Solsperse 2400, disponible comercialmente en Avecia 56,0 gramos (35,65%)  Perlas Zircoa 1 mm 70,0 gramos (44,56%) 35HDTLV, de Rhodia Inc. 36Catalizador Metacure T-12, disponible comercialmente en Air Products y Chemicals, Inc. 2930% silica nanoparticles / 70% siloxane. 30Eastman Chemicals. 31 Acrylic resin with hydroxyl functionality. 32 Exxate 600 solvent (hexyl acetate) from Union Carbide. 33 Carbide Union. 3463.4% of particulate paste prepared by mixing the following:  Goresil 25 56.0 grams (35.65%)  Methyl amyl ketone 21.0 grams (13.37%)  Acrylic resin with hydroxyl functionality 10.0 grams (3.37%) ols Solsperse 2400, commercially available in Avecia 56.0 grams (35.65%)  Zircoa pearls 1 mm 70.0 grams (44.56%) 35HDTLV, from Rhodia Inc. 36 Metacure T-12 Catalyst , commercially available from Air Products and Chemicals, Inc.

Los componentes de la pasta de partículas se sellaron en un frasco de 8 onzas y se agitaron en un agitador de pintura durante 3,5 horas para dispersar la pasta de partículas. Los medios de molienda se separaron por filtración y el material 5 estaba preparado para ser usado. Los ingredientes anteriores se mezclaron y se pulverizaron antes de 10 minutos debido a la corta vida de la mezcla, lo cual es normal para los sistemas de reacabado de dos componentes. The components of the particle paste were sealed in an 8-ounce jar and stirred on a paint shaker for 3.5 hours to disperse the particle paste. The grinding media were filtered off and the material 5 was ready to be used. The above ingredients were mixed and sprayed within 10 minutes due to the short life of the mixture, which is normal for two component refinishing systems.

Los paneles de imprimación de color negro ED5051 descritos en el Ejemplo 1 se pulverizaron a mano a 3,1 105 Pa (45 ps, 22°C (71,6°F), y 63 por ciento de humedad relativa, y se curaron al aire. Los paneles se ensayaron después de una semana para proporcionar un curado suficiente. Los ensayos realizados y los resultados se muestran en la Tabla 19. The ED5051 black primer panels described in Example 1 were hand sprayed at 3.1 105 Pa (45 ps, 22 ° C (71.6 ° F), and 63 percent relative humidity, and cured at air The panels were tested after one week to provide sufficient cure The tests performed and the results are shown in Table 19.

10 Tabla 19 10 Table 19

Descripción Description
Muestra 15 Muestra 16 Muestra 17 Sample 15 Sample 16 Sample 17

Brillo inicial a 20º Initial brightness at 20º
83,1 81,8 81,7 83.1 81.8 81.7

Papel 9μ 9μ paper
51 46 67 51 46 67

Papel 3μ 3μ paper
66 73 78 66 73 78

(Cont.) (Cont.)

Papel 2μ 2μ paper
84 90 89 84 90 89

BON AMI BON AMI
79 96 94 79 96 94

Lana de acero 0000# (10x); dispositivo de ensayo Atlas Steel wool 0000 # (10x); Atlas test device
62 84 76 62 84 76

El uso de las presentes partículas en el sistema de revestimiento líquido (Muestras 31 y 32) imparte una resistencia mejorada a la abrasión y al rayado en comparación con el control (Muestra 30). The use of the present particles in the liquid coating system (Samples 31 and 32) imparts improved abrasion and scratch resistance compared to the control (Sample 30).

5 Ejemplo 10 (No es un ejemplo según la presente invención) 5 Example 10 (Not an example according to the present invention)

Los paneles se revistieron y se ensayaron tal como se ha descrito en el Ejemplo 1, usando los revestimientos indicados en la Tabla 20. La carga de partículas fue del 0,3% para las Muestras 34-36, y del 0,1% para la Muestra 37. Los paneles se sometieron a exposición a QUV durante 500, 1.000 o 1.500 horas según ASTM D-4587. Tal como se ilustra en la tabla, las presentes composiciones que contenían partículas mostraron una mejor resistencia al rayado después de la exposición a The panels were coated and tested as described in Example 1, using the coatings indicated in Table 20. The particle loading was 0.3% for Samples 34-36, and 0.1% for Sample 37. The panels were exposed to QUV for 500, 1,000 or 1,500 hours according to ASTM D-4587. As illustrated in the table, the present compositions containing particles showed a better scratch resistance after exposure to

10 QUV en comparación con el control que carece de partículas, y en muchos casos una resistencia mejorada al rayado conforme se aumentó la duración de la exposición a QUV. Los resultados en la tabla se proporcionan en % de retención de brillo usando brillo a 20º. 10 QUV compared to the control lacking particles, and in many cases an improved scratch resistance as the duration of QUV exposure was increased. The results in the table are provided in% gloss retention using brightness at 20 °.

Tabla 20 Table 20

Muestra 33 DJ5537 Sample 33 DJ5537
Muestra 34 DJ55 W210 Muestra 35 DJ55 WCA3 Muestra 36 DJ55 Goresil 25 Muestra 37 DJ55 polvo de diamante MBM 4-8 Sample 34 DJ55 W210 Sample 35 DJ55 WCA3 Sample 36 DJ55 Goresil 25 Sample 37 DJ55 diamond dust MBM 4-8

Papel 2μ inicial Initial 2μ paper
62,6 72,2 90,3 72,9 85,9 62.6 72.2 90.3 72.9 85.9

500 horas 500 hours
77,4 94,1 96,9 95,6 93,1 77.4 94.1 96.9 95.6 93.1

1.000 horas 1,000 hours
76 94,7 94,3 91,7 94,6 76 94.7 94.3 91.7 94.6

1.500 horas 1,500 hours
92,8 92,2 97,4 97,6 91,1 92.8 92.2 97.4 97.6 91.1

Papel 9la inicial Paper 9the initial
13,6 20,1 28,2 19,0 77,7 13.6 20.1 28.2 19.0 77.7

500 horas 500 hours
11,7 17,6 45 17 77,7 11.7 17.6 Four. Five 17 77.7

1.000 horas 1,000 hours
21,9 20 57 30,4 82,4 21.9 twenty 57 30.4 82.4

1.500 horas 1,500 hours
40,1 35,6 72,5 42,7 68,1 40.1 35.6 72.5 42.7 68.1

37Revestimiento acrílico en polvo, disponible comercialmente en PPG Industries, Inc. 37 Acrylic powder coating, commercially available from PPG Industries, Inc.
15 Ejemplo 11 15 Example 11

Las muestras 38-44 se prepararon y se ensayaron tal como se describe en el Ejemplo 5, usando los componentes mostrados en la Tabla 21. El uso de partículas tratadas térmicamente (Muestras 42, 43 y 44) generalmente proporcionó mejores resultados que sus homólogos no tratados térmicamente (Muestras 39, 40 y 41, respectivamente), que todavía proporcionaron un mejor rendimiento general que la Muestra 38 de control, que no tenía partículas. Samples 38-44 were prepared and tested as described in Example 5, using the components shown in Table 21. The use of heat treated particles (Samples 42, 43 and 44) generally provided better results than their non-counterparts. heat treated (Samples 39, 40 and 41, respectively), which still provided a better overall performance than Control Sample 38, which had no particles.

20 twenty

Tabla 21 Table 21

Muestra 38* Sample 38 *
Muestra 39* Muestra 40 Muestra 41* Muestra 42* Muestra 43* Muestra 44* Sample 39 * Sample 40 Sample 41 * Sample 42 * Sample 43 * Sample 44 *

Resina acrílica GMA GMA acrylic resin
79,76 77,98 77,98 77,98 77,98 77,98 77,98 79.76 77.98 77.98 77.98 77.98 77.98 77.98

DDDA DDDA
17,51 17,12 17,12 17,12 17,12 17,12 17,12 17.51 17,12 17,12 17,12 17,12 17,12 17,12

Micropolvo cera C Micropowder wax C
0,53 0,52 0,52 0,52 0,52 0,52 0,52 0.53 0.52 0.52 0.52 0.52 0.52 0.52

Benzoína Benzoin
0,38 0,37 0,37 0,37 0,37 0,37 0,37 0.38 0.37 0.37 0.37 0.37 0.37 0.37

Catalizador trifeniltrihidróxido Triphenyltrihydroxide catalyst
0,91 0,89 0,89 0,89 0,89 0,89 0,89 0.91 0.89 0.89 0.89 0.89 0.89 0.89

Modaflow Modaflow
0,91 0,89 0,89 0,89 0,89 0,89 0,89 0.91 0.89 0.89 0.89 0.89 0.89 0.89

Sunspheres 05 Sunspheres 05
- 2,22 - - - - - - 2.22 - - - - -

T64-2038 T64-2038
- - 2,22 - - - -- - - 2.22 - - - -

Zeeospheres W210 Zeeospheres W210
- - - 2,22 - - -- - - - 2.22 - - -

HT39 Sunspheres 05 HT39 Sunspheres 05
- - - - 2,22 - -- - - - - 2.22 - -

HT T64-20 HT T64-20
- - - - - 2,22 -- - - - - - 2.22 -

HT Zeeospheres W210 HT Zeeospheres W210
- - - - - - 2,22 - - - - - - 2.22

Brillo 20º inicial Initial 20 Brightness
83,0 82,8 79,1 77,1 82,7 79,1 76,9 83.0 82.8 79.1 77.1 82.7 79.1 76.9

Papel 9μ 9μ paper
13,6 16,7 62,5 44,4 28,4 67,8 50,3 13.6 16.7 62.5 44.4 28.4 67.8 50.3

Papel 3μ 3μ paper
31,1 29,7 83,3 77,4 57,9 88,5 76,7 31.1 29.7 83.3 77.4 57.9 88.5 76.7

BON AMI (20x) BON AMI (20x)
79,4 93,8 92,6 97,5 96,4 94,6 98,1 79.4 93.8 92.6 97.5 96.4 94.6 98.1

Lana de acero calibre 0000# (5x, martillo ligero) 0000 # steel wool (5x, light hammer)
83,1 87,8 92,8 98,8 95,8 97,7 98,8 83.1 87.8 92.8 98.8 95.8 97.7 98.8

Lana de acero calibre 0000# (5x, martillo pesado) 0000 # (5x, heavy hammer) steel wool
83,0 87,6 91,2 87,1 90,7 95,2 97,5 83.0 87.6 91.2 87.1 90.7 95.2 97.5

* No es una muestra según la invención 38Alúmina tabular, tamaño medio de partícula 7μ, tamaño máximo de partícula 20μ, disponible comercialmente en Alcoa. 39"HT" = tratado térmicamente durante tres horas a 700°C. * No una muestra según la presente invención * It is not a sample according to the invention 38 Tabular alumina, average particle size 7μ, maximum particle size 20μ, commercially available from Alcoa. 39 "HT" = heat treated for three hours at 700 ° C. * Not a sample according to the present invention

Claims (1)

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